Process of manufacturing quinhydrone



Jam 8, 1935- K. c. KLEIMENHAGEN 1,987,148'

PROCESS OF MANUFACTURING QINHYDRONE Filed Feb. l19, 1934 /fA/H .772 @MDW/AGEN :Inman/13s Patented Jan. 8, 1935l PROCESS onY MANU'lino'rulmvq` v QUINHYDRONE 'Karl'ohristian meinienhagen, La sans, nl., alsignor to Carusv Chemical Co.,`Inc., Saille';`

l Animation-Febuary 19,1934;seiiai-Nai'ziiosi- "momias k(o1.260556)- invention relates to the commercial'production of' quinhydrone. n While this corn-pound* has-various uses, suchas a mordantv for'silkg' it isoi primary y importance 'becausellof they 'fact "lAA that it is a;V very desirable?! and"corv'eanieI-i'tcoz-hfA l poundf from, which* hydroquinone-ca'nhel in'a'd'e" see patents to Efesini-inn:I Einde 11,532,800 a'iid 1,540,738) and hydroquiho'neacq'ired' a'n'firn'- portant statustl'e photographicindustry;.alsa

?' photographicdeveloper;

-In1 general, quinhydrone isiprotuced theyre-k ductionf: oi quinoney ay suitablereducingi agent or by allowing solutions of quinone and hydro? H quinoneto'lreact, forming quinhydroneby'single qinone or' quinhydroneY itselfg" rthis niethod` is: 'oflittle?commercialimportance:A "f f Wliileiquinonev can` be lre'diicedy directly; to7 hydroquinon; thep'roductionrof ai pure'y quinone, f

as Will hereinafter be related,,isidifllcultv` v The general, well-known method for `producingy quinone is bythefoxidation offanilinezin an. aqueous sulfuric f acid` solution i With-either mani ganese dioxide or sodium dichromate, at. temf peraturesbelow 6:- centigrade.' A VVOneV ofT the methods: Iof..separationm ofn the quinone rfromthe. oxidationmixturevisby extrae,

tion.- withr also1vent,. as.. forv example,n ether. This method, howeverfis.notsatisfactory asthesolvent and aqueous portions do not separate. yin satis?, factory layers. Several extractions must be made. This. process is` long, tedious, and-there arealso .the usual.` solvent hazards -as wellas losses.4 Y

Another rnethod is to heat the oxidationlfniix'- When' a crude y quinone oi'iid'ation liquid is lfieat'i'ed,l strong, quinonel vapors areievol'ved) Even V at temperatinesh considerabl-yfbelow' thez boiling rate'tl'at'tl'ie cooling' fumes LAabove -tlie'liquidi l'condnse-ir'i"-a'snow-1c1oud of quino'nef. This property vkthis'patent, byheating a crude oxidationr addition. ofi these twovr compounds.- vIEt.rr1'ay",l for' the sake of" convenience,- also be* prepared= bygthe f' oxidation' of' hydroquinone.:` -This is=;,thefusua1 method for' making:` small`- quantities;` but since hydroqui'nonefis vmadel byl ,the reduction of" The insoluble impuritemperatures and f the' obnoxious `quinone furnesl point, the quinone is given off?. at such aco`1oiousvv when irre c'ruae quiiiiiefsluiiiifisfiiieat its' boiling point., the therein is rp'imy deff comporti',,andihieldiiaiderbrf rapid decomposition' takes p foundf that @suitable te'iii'perat e is"Y and i'neficient;` yThe liquid" becomes* warmjanqg 35j quinone lis 10st through deornppjsitiiif and" vo g; tilization. Instead yof.attempting to2-k qunone tlieroth'er liquor' orina v v extraction necessary-r Ii?listhus;` SentHwf', usual rnethodsof preparing a* pure q'umone fini` the further use of "preparing eitherqiiinlydrone l quinone known tothe trade as the oxidation operation' o i Crilde .quinonerliqudontening, 19t @mmml.e,` 10Q-:Dwnlds 0f quinone ispumped into the vesselL A vand a solutionl of hydroquinone .containing at least 1 00 pounds Vof -hy droq1 1inone,.but preferably -mixture which may be heated with live steam .Y entering through pipe C.

be formed in any other suitable apparatus." a closed receiving Vessel partly i'llled with"'a` strong aqueous solution ofV hydIQqlliIlQIieg; "l'llt-L` 1 solution should be concentrated but somewhat" below the saturation point to preventtcrystallizati'on. The vapor pipe Dgenters the, receiver and terminates at a distance' below "the level of the hydroquinone solution. This distance varies accordingto the all'shlil'teA pressure. thatfl is to be maintained in vessels A and B.. `E is. aV circulating pump of suiiicient size that" pumpsl the hydroquinonefsolutioninto therdowncomine vapor pipe throught@ .Suitable spray vriozzleli, whi ch no zzlel visyat; such a distance abovel the Qutlet, 01?; the lavoro .thatthequmone vapors will befrreciiellyfall. c nden'sedhytheorculating lhydroouino-neI solution: G isfan exhaust f water-vapor pipe connectedto a standardsuitable Wateravaporcondenser and.. vacuum pump,...

quinone solutionv :enters the V receiverwB- l s l H isapipe connectionlthroughnwhich thehydro-` 200 pounds, is added tothe receiver- B andfsuilicintiwater added Sorthatrinthis:particular ex-,

ample, the outlet-.ofther vapor pipewillif b e lap- D10Ximate1y-two; feety below the surface l of ,ther Y liquid. 'I'hereceiver-isjthen put under a .vacuum of .271/2 inches of mercury. Dueto the'f'actthat the ,Outlet 0fy thevacuumf pipe 1 is approximately. two feet below the surface of the liquid, thel Vacuum `"essel A will. be approximately .251/2 inches. The circulating pump lis now started andlthe crude quinone-liquid heated. Whenthe temperature reaches around 54Ucentigrade the liquid `will start to: boil. The vapors at about approximately thistemperatureenter the vapor pipe andare condensedby the spray of cool hydroquinone liquid entering the `vapor -pipe through nozzle F. v The .condensed quinone com- .binesf immediatelywith the yhydroquinone ito formquinhydrone andIallsinto the-liquid ini the, receiver. .The s olutionv intthe `receiver gradually warms upguntil it` reaches the boil-j ing-point Ac orresporiding to `v`the `vacuum maintained `iinthe receiving v vessel. The temperaturefin this particular example would be` approximately 42".centigrade.r v-When this temlperature is reached. it alsostarts to boil and the temperature will not ..rise appreciably higherl as long as the Vacuum-is;maintained; The vvapors rising from thelsolution are watervapors practically free from quinone. -Thekvolume `of the solution in thereceiver willalso not appreciably changesince y the water is boiled-oli? at nearly thefsame rate -atwhich the-,water vapors come over..y from theyessel A. Since quinhydronefgis only slightly soluble at this temperature, quin-` hydrone crystals vform-in the receiver, but these-k being very small and, light in vweight,do not interferawithrthe.pump or the working of'zthe,

-uid with ease, washedand dried in the usual manner, or reduced to hydroqunone by any of A the well known means, or it may be reduced in .the receiver itself 4`to' hydroquinone bya method similar to that of Emde in Patent 1,540,738. The

yield of quinhydrone is almost theoretical when based on the quantity of quinone entering the VKLDQI'-Dlle-y The above is 'merely an example showing the operation of my invention and I do not limit my invention tothe above temperatures and pressures, but it is desirable to maintain such a vacuum in the receiver as to prevent the temperature ofIsolutionfftherein from rising above 65 rcentigrade.. For example, the distillation in vessel A may take place at atmospheric pressure and at al temperature of around .100 centigrade and a vacuum of y29 inches oi?V mercury with a corxje-v spending temperature of approximately -25 centi.`

grade may beVV maintained in the receiver; This; cambe accomplishedby.havinsltheioutlet of the Victorino?. at, asumcientidistance' belowv` the, topf level ofj the-liquid in the receiver, which distance can'lbe readily determined;

The absolutepressure in-vesseLB must always :"5 4be less than the absolute pressure'in vesselA in Having 'newA described the essence .of the apparinbplefof ts- 'order thatthep'solution invessel Byvillalways be ,kept at a 'temperature below'that ofthe qumgne `lv`vapor.j Y v' V- v couldnot be' foreseen, however, that when'asolution J of quinhydrone VVorrasoluti'on lof :hydro-A` quinon'e'with quinhydrone. therein could belefl'r` boiling under a reducedpressureat temperatures below" approximately; 65f c entigrade,v the v"lossff of quinone therefrom' -would be atla 'negligiblerate I claim asmy'invention:r

1`. The 'process "ormakmg quinhydrone wlii'cn comprisesA c ondensingiquinone vapors with'a` so-'` lution offhydroquinone ata substantially lower:

temperature.A

2. The process of'makingouinhydrone which comprises condensing quino'nevaporsbyr contacting said vaporswith a'solution of hydroquinone, which solution is kept below 65 degrees C; by subjecting it `to a `vacuun'i greaterfthan '1225/2- inches 3. The process of making'quinhydrone comprises condensing 4quinone vapors by 'contactingsaidvapors with a solution oi.' hydrocluinone which solution is at a lower temperature than the'quinonevapor and not exceeding'y centigrade.

,4. The process comprises condensingfquinone vaporswith a recirculating rhydroquinone solution, which solution,y

ature below' .that of the'quinonevapor by sulziject-` ingr it to avacuum greaterthan A221/21inches of mercury. f

of makingVVK quinhydrone which 5. The process of concentratinga quinhydronesolution without appreciable loss oi'quinone therefrom comprising boilingsaid solution at a tem-j.

perature below C. and under-avacuum greater than 2 21/2 inches oil-mercury.` 1 y 6. The process of producing quinhydrone which comprises steam distilling an oxidation mixture of quinone, and condensing said vapors by contact with a solution of hydroquinone, and maintaining the temperature of said solution within the temperature range at which the quinone vapors are substantially stable.

7. The process of producing quinhydrone which comprises steam distilling an oxidation mixture of quinone, condensing said vapors by Contact With a solution of hydroquinone at a temperature below 65 degrees C. and collecting the crystals of quinhydrone so formed in the hydroquinone solution.

8. The process of making quinhydrone comprising condensing quinone vapors with a solution of hydroquinone and maintaining the temperature of said solution Within the temperature range at which the quinone vapors are substan-l tially stable.

9. The process of making quinhydrone which comprises condensing quinone vapors with a solution of hydroquinone and maintaining the temperature of said solution appreciably below that of the vapors by keeping saidsolution under a suitable vacuum.

10. The process of making quinhydrone which comprises condensing quinone vapor with a solution of hydroquinone and maintaining the boiling point of the solution Within predetermined limits by subjecting the solution to vacuum greater than twenty-two and one-half inches of mercury.

KARL CHRISTIAN KLEIMENHAGEN. 

